MnOx-TiO2吸附剂对燃煤烟气中汞的脱除

李扬; 刘冰; 杨赫; 杨大伟; 胡浩权

MnO_x-TiO₂吸附剂对燃煤烟气中汞的脱除

李扬^1, ,,
刘冰¹,
杨赫¹,
杨大伟²,
胡浩权¹

1.
大连理工大学化工学院煤化工研究设计所, 精细化工国家重点实验室, 辽宁大连 116024
2.
辽宁省朝阳市朝阳县环境保护局, 辽宁朝阳 122000

基金项目:

国家自然科学基金面上基金项目 21776039

国家自然科学基金青年科学基金项目 51306028

中央高校基本科研业务费 DUT2018TB0

详细信息

中图分类号: X511
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- 被引次数: 0
出版历程
- 收稿日期: 2020-01-13
- 修回日期: 2020-03-23
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-05-10

Removal of elemental mercury (Hg⁰) from simulated flue gas over MnO_x-TiO₂ sorbents

1.
State Key Laboratory of Fine Chemicals, Institute of Coal Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
2.
Environmental Protection Bureau of Chao Yang County, Chaoyang 122000, China

Funds:

the National Natural Science Foundation of China 21776039

National Natural Science Foundation for Young Scientist of China 51306028

the Fundamental Research Funds for the Central Universities DUT2018TB0

More Information

Corresponding author: LI Yang, Tel: 13478914680, E-mail:yli@dlut.edu.cn

摘要

摘要: 以锐钛矿型TiO₂为载体，采用浸渍法对其进行MnO_x改性制备脱汞吸附剂，探究了负载量、焙烧温度、反应温度及烟气组分等参数对吸附剂脱汞性能的影响。利用N₂吸附-脱附、TG/DTG、XRD、FT-IR、Hg-TPD、XPS等方法对吸附剂的理化性质进行了表征。结果表明，Mn的最佳负载量为12%，最佳焙烧温度和反应温度分别为450和300 ℃，在实验条件下MnO_x-TiO₂吸附剂可达到的最佳脱汞效率为98.46%。烟气中少量的O₂及微量的HCl对吸附剂的脱汞有较强的促进作用；SO₂对吸附剂的脱汞有较强的抑制作用，SO₂与Hg⁰存在的竞争吸附作用以及脱汞反应中产生的硫酸盐覆盖活性位点表面，是导致脱汞效率下降的主要原因。烟气中的CO₂和NO也会对汞的脱除产生轻微的抑制作用。负载在吸附剂上的MnO_x存在Mn⁴⁺、Mn³⁺两种价态，其中，Mn⁴⁺将Hg⁰氧化为Hg²⁺，自身被还原为Mn³⁺。结合实验和分析结果发现，Hg⁰的吸附和氧化基本遵循Mars-Maessen和Langmuir-Hinshelwood机理。
- 模拟烟气 /
- 吸附剂 /
- 脱汞 /
- MnO_x /
- TiO₂
Abstract: A series of MnO_x modified TiO₂ based sorbents were synthesized using wet impregnation method and its performance on elemental mercury (Hg⁰) removal was studied. The effects of loading amount, calcination temperature, reaction temperature, and flue gas compositions on mercury removal efficiency were investigated. The sorbents were characterized by TGA, N₂ adsorption-desorption, XRD, FT-IR, XPS and Hg-TPD. It was shown that the optimum MnO_x loading value was 12%, and the optimal calcination and reaction temperature were 450 and 300 ℃, respectively. The highest mercury removal efficiency of MnO_x-TiO₂ sorbent was 98.46%. O₂ and HCl in flue gas played a positive role in mercury removal. SO₂ had a strong inhibitory effect on mercury removal, which may be due to the competition adsorption between SO₂ and Hg⁰. At the same time, the manganese sulfate produced during the reaction covered the surface of the active site, resulting in the decrease in mercury removal efficiency. CO₂ and NO in flue gas also slightly inhibited mercury removal. Mn⁴⁺ participated in oxidizing Hg⁰ to Hg²⁺, accompanied with its reduction to Mn³⁺. The adsorption and oxidation process of Hg⁰ over MnO_x-TiO₂ basically conformed to the Mars-Maessen mechanism and Langmuir-Hinshelwood mechanism.
- simulated flue gas /
- sorbent /
- mercury removal /
- MnO_x /
- TiO₂

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图 1 实验装置流程示意图

Figure 1 Schematic diagram of experimental apparatus

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图 2 12Mn-Ti的TG/DTG曲线

Figure 2 TG/DTG curves of 12Mn-Ti

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图 3 Mn-Ti-450的吸附等温线及孔径分布

Figure 3 physisorption isothermal and pore size distribution of Mn-Ti-450

(a): N₂ adsorption-desorption isotherm; (b): pore size distribution

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图 4 12Mn-Ti-t的吸附-脱附等温线及孔径分布

Figure 4 N₂ physisorption isothermal and pore size distribution of 12Mn-Ti-t

(a): N₂ adsorption-desorption isotherm; (b): pore size distribution

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图 5 样品的XRD谱图

Figure 5 XRD patterns of sorbents

(a): Mn-Ti-450 with Mn loading value of 1-12; (b): 12Mn-Ti with calcination temperature of 400-500 ℃

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图 6 样品的FT-IR谱图

Figure 6 FT-IR patterns of sorbents

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图 7 12Mn-Ti-450的XPS谱图

Figure 7 XPS spectra of 12Mn-Ti-450

(a): Mn 2p of fresh and spent sample; (b): O 1s of fresh and spent sample; (c): Ti 2p of fresh and spent sample; (d): Hg 4f of spent sample in BFG atmosphere; (e): Hg 4f of spent sample in (BFG+0.4‰ SO₂); (f): S 2p of spent sample in (BFG+0.4‰ SO₂)

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图 8 Mn负载量对脱汞性能的影响

Figure 8 Effect of Mn loading value on Hg⁰ removal

(reaction temperature t=200 ℃, BFG)

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图 9 焙烧温度对12Mn-Ti-t脱汞性能的影响

Figure 9 Effect of calcination temperature on Hg⁰ removal over 12Mn-Ti-t

(reaction temperature t=300 ℃, BFG)

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图 10 反应温度对12Mn-Ti-450脱汞性能的影响

Figure 10 Effect of reaction temperature on Hg⁰ removal over 12Mn-Ti-450

(reaction temperature t=150-350 ℃, BFG)

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图 11 烟气组分对12Mn-Ti-450脱汞性能的影响

Figure 11 Effect of gas components on Hg⁰ removal over 12Mn-Ti-450

(a): removal efficiency; (b): adsorption capacity
(reaction temperature t=300 ℃, 0-10% O₂, 0-12% CO₂, 0-0.4‰ SO₂, 0-0.02‰ HCl, 0-0.4‰ NO, N₂ as balance gas)

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图 12 反应时间(a)、反应温度(b)、酸性气体(c)对12Mn-Ti-450氧化Hg⁰效率的影响

Figure 12 Effects of reaction time (a), reaction temperature (b), acid gas (c) on Hg⁰ oxidation efficiency over 12Mn-Ti-450

reaction condition: (a): BFG, 300 ℃; (b): BFG, 200/250/300 ℃; (c): BFG, BFG+0.2‰ SO₂, BFG+0.2‰ NO, 300 ℃
: Hg²⁺; : Hg_ad

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图 13 12Mn-Ti-450反应3 h后的Hg-TPD谱图

Figure 13 Hg-TPD patterns of 12Mn-Ti-450 after reaction at 300 ℃

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表 1 Mn-Ti-450的比表面积及孔隙参数

Table 1 Surface area and pore parameters of Mn-Ti-450

Sample	A_BET/(m²·g^-1)	v_t/(cm³·g^-1)	d_ave/nm
TiO₂	94.3	0.400	13.1
1Mn-Ti-450	90.7	0.366	11.5
3Mn-Ti-450	87.4	0.370	12.5
5Mn-Ti-450	84.3	0.373	12.4
8Mn-Ti-450	83.7	0.357	13.0
10Mn-Ti-450	81.2	0.351	13.3
12Mn-Ti-450	80.3	0.353	13.2
12Mn-Ti-400	80.2	0.366	11.5
12Mn-Ti-500	75.8	0.365	13.8

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表 2 12Mn-Ti-450反应前后样品表面Mn相对含量

Table 2 Surface Mn concentration of fresh and spent 12Mn-Ti-450

Sample	Surface atomic ratio /%
Sample	Mn⁴⁺	Mn³⁺	Mn²⁺
Fresh	35.7	64.3	-
Spent	30.5	69.5	-
Spent-SO₂	26.0	52.5	21.5

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表 3 12Mn-Ti-450反应前后样品表面O相对含量

Table 3 Surface O concentration of fresh and spent 12Mn-Ti-450

Sample	Surface atomic ratio /%
Sample	O_α/(O_α+O_β)	O_β/(O_α+O_β)
Fresh	84.4	15.6
Spent	87.9	12.1
Spent-SO₂	72.4	27.6

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